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The crop rotation is a practice to protect and improve the soil properties and an alternative to improve the quality of crop residues is the application of fertilizers at the planting of cover crops. Thus, we evaluated the effect of fertilization with nitrogen, phosphorus and potassium (NPK) on organic matter production and chemical composition of cover crops succeeding the corn crop. The treatments consisted of the cultivation of Avena sativa L., Lupinus albus L., Pennisetum glaucum L., Raphanus sativus L. and Sorghum bicolor L. with (200 kg ha−1 of NPK [08-28-16] applied by broadcast seeding) and without fertilization at planting. Organic matter production by all cover crops, as well as concentrations of neutral detergent fibre (NDF) in shoots and roots of A. sativa L. and R. sativus L. were higher when they were fertilized. L. albus L. showed higher NDF and acid detergent fibre (ADF) contents than the other cover crops, with and without fertilization. Nitrogen concentration increased, but the carbon/nitrogen ratio (C/N) in the shoots of L. albus L., R. sativus L. and S. bicolor L. decreased when fertilization was applied. The use of N by the A. sativa L. and P. glaucum L. and of P and K by S. bicolor L. was 16, 54, 82 and 20% more efficient, respectively, when fertilization was applied. The A. sativa L., P. glaucum L. and R. sativus L. showed higher NDF/N, ADF/N and hemicellulose/N ratios in the fertilized treatment. Although the results obtained in this study are highly satisfactory, more research should be conducted to evaluate the decomposition of crop residues from cover crops fertilized with NPK, and the effects of this strategy on corn crops in succession.